Polymerizable urethane compounds

ABSTRACT

Ethylenically unsaturated urethane monomers containing three or more double bonds per molecule and addition polymers and copolymers of these compounds are disclosed.

Unite tates l aten [1 IIelIII Dec. 24, 19M

[ POLYMERIZABLE URETHANE [56] References Cited WMPOUNDS FOREIGN PATENTS OR APPLICATIONS [75] Inventor: Erich Kuelm, Wilmington, Del. 1,916,499 11/1969 Germany I 1 Assignee= Atlas Chemical Industries, lililjiil 511323 22127311511131:11:11:11 32311333 Wilmington, Del.

[22] Filed: Dec, 23, 1971 Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Paul J. Killos [211 App! 211L670 Attorney, Agent, or FirmlCl United States Inc.

[52] US. Cl 260/4045, 260/76, 260/404, [57] ABSTRACT 260/4105 260/471 260/475 260/482 Ethylenically unsaturated urethane monomers con- [5 I t U 260/485 q f g taining three or more double bonds per molecule and I1 C l 1 f h 58 Field! of Search 260/486, 482 B, 471 c, a p0 Ymers and cop) ymers 0 ese Com 260/404 5 pounds are disclosed.

7 Claims, N0 Drawings l POLYMERIZABLE IURETHANE COMPOUNDS This invention relates to ethylenically unsaturated monomers, the homopolymers and copolymers ofthese monomers, and mixed resins prepared from these monomers and unsaturated polyesters. More particucally unsaturated monomers containing at least three double bonds.

It is another object of this invention to provide novel polymers from ethylenically unsaturated monomers containing at least three double bonds.

It is another object of this invention to provide homo- 5 polymers and mixed resins suitable for forming molded plastic products and fiber reinforced plastic products and laminates prepared by using an ethylenically unsaturated monomer containing at least three double bonds.

(monomer resins) of this invention are comprised of the reaction product of (a) an organic polyisocyanate having at least 3 isocyanate groups, and (b) a stoichiometric quantity of a hydroxyl terminated ethylenically unsaturated ester for reacting with each of said isocyanate groups. A preferred group of monomers or unsaturated urethane compounds may be represented by the formula:

1) H o v o I It I! 4 5 R-N-c-o-R -o-cR iwherein R is a residue of a polyfunctional organic isocyanate which contained at least m isocyanate groups, m is at least about 3, R is selected from the group consisting of alkylene radicals which contain at least 2 carbon atoms, a radical resulting from the removal of 2 hydroxyl groups from a cycloaliphatic diol, a radical resulting from the removal of 2 hydroxyl groups from an etherified diphenol and a radical resulting from the removal of 2 hydroxyl groups from an ethylenically unsaturated diol and R is an alkenyl radical containing from about 3 to 18 carbon atoms, provided that the sum of the carbon atoms in R, and R is from about 5 through about 48.

Novel homopolymers and copolymers of the present invention are prepared by the polymerization of monomers within the formula represented above with or without other ethylenically unsaturated monomers in the presence of or absence of free radical catalysts.

Among the mixed resins of this invention are those comprised of the addition polymerization products of ne(3)-2-bromo-4-hydroxyphenyl the ethylenically unsaturated monomer represented by the above Formula (I) and an ethylenically unsaturated polyester resin. The polyester resin can be the condensation product of an unsaturated dicarboxylic acid and an etherified diphenol which can be represented by the formula EE EE EE EE wherein z is 0 or 1; R is an alkylcne radical containing from I to 5 carbon atoms, oxygen, sulfur, or a divalent radical which may be represented by the following formula R, is ethylene or propylene; each E is individually selected from hydrogen atoms and halogen atoms; and .r

and y are integers from I through about 20 with the proviso that the sum of x and y is from about 2 through about 30. Any of the well known suitable ethylenically unsaturated dicarboxylic acids can be used to prepare the present polyester resins by condensation with a diol represented by Formula (2). For example among those acids that can be used are maleic acid, fumaric acid or the anhydride of maleic acid. Examples of compounds within the above general Formula (2) are polyoxypropylene(2)-2,2-bis(4-hydroxyphenyl) propane; polyoxyethylene(3)-2,2-bis(4-hydroxyphenyl) propane; polyoxypropylene(3)-bis(4-hydroxyphenyl) thioether; polyoxyethylene(Z)-2,6-dichloro-4-hydroxyphenyl 2',3,6- trichloro-4-hydroxyphenyl methane; polyoxypropyle- 4-hydroxyphenyl polyoxyethylene( 2.5 )-4,4- isopropylidenediphenol; polyoxybutylene(4)-bis(4- hydroxyphenyl) ketone; polyoxypropylene(3)-2,2- bis(2,6-diiodo-4-hydroxyphenyl) propane; and polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl) propane.

As stated above the present urethane monomers repether;

resented by Formula l above are polymerizable with ethylenically unsaturated polyesters. In addition to polyesters prepared from the above described diol and dibasic acid reactants other suitable ethylenically unsaturated polyester resins can be prepared from either an ethylenically unsaturated dicarboxylic acid and a saturated diol, or an ethylenically unsaturated diol and a saturated dicarboxylic acid, or both the diol and the dicarboxylic acid can be ethylenically unsaturated. Among the additional diol reactants that can be used are the straight or branched chain alkane diols and the cycloaliphatic diols as well as such diols that are halogen substituted having from 2 to 12 carbon atoms. Unsaturated aliphatic diols containing from 2 to l0 carbon atoms can also be used. For example among the diols that can be used are ethylene glycol, l,4-butylene glycol, l,6-hexylene glycol, neopentyl glycol, l,4- cyclohexanedimethanol, 2,5-dimethyl-2,5-hexanediol, and the monoallyl ether of glycerin. Among the other acids that can be used to prepare the subject polyester resins are o-phthalic acid, isophthalic acid, adipic acid, sebacic acid, succinic acid and azelaic acid. Suitable halogenated derivatives of such acids can also be used to prepare the subject unsaturated polyester resins. Ex-

amples of the polyesters contemplated as useful in preparing mixed resins with the urethane monomers of this invention are the following: neopentyl glycol fumarate, propylene glycol maleate, dibromobutenediol succinate, polyoxypropylene (l6)-2,2-bis(4-hydroxyphenyl)- propane fumarate, and polyoxyethylene(2.2)-2,2-bis (2,6-dichloro-4-hydroxyphenyl)propane fumarate.

In general the above noted unsaturated polyester resins can be prepared by reacting a suitable dicarboxylic acid with a suitable diol such as one of the above described etherified diphenols at a temperature of about 200C. or more under an inert atmosphere. Known catalysts or promoters used in preparing polyesters, for example p-toluenesulfonic acid, can be added in catalytic amounts to enhance to activity of the particular reactants if indicated. Suitable catalysts, for example p-toluenesulfonic acid is used at a concentration of from about 0.005% to 0.3% by weight based on the weight of the reaction mixture. The ratio ofthe number of hydroxyl groups of said diol to the number of carboxyl groups of said dicarboxylic acid may be from about 12:08 to 0.821 .2 but is preferably about 1:1.

OCN (CH 6 CH CH CH -CH I I I NCO NCO NCO sented by Formula (I), are prepared from polyfunctional isocyanates and hydroxyl terminated unsaturated monoesters. By the terms polyfunctional isocyanate or organic polyisocyanate as used herein is meant aromatic or aliphatic isocyanates having at least 3 isocyanate groups per molecule. Exemplary of these polyisocyanates are polymethylene polyphenyl isocyanates, such as those sold under the trade names PAPl and MONDUR MR, 4,4'4"-triphenylmethane triisocyanate; 2,4,6-toluene triisocyanate; 4,4-dimethyl diphenyl methane 2,2,5,5-tetraisocyanate, and condensation products of diisocyanates prefcrrably aromatic diisocyanates with water, and polyols including diols, triols, hexitols and alkylene oxide derivatives (ethers) of these polyols to yield polyisocyanates containing 3 or more free NCO groups. These polyisocyanates and processes for the preparation thereof are known in the art as exemplified by the disclosures of German Pat.

No. 1,150,518; British Pat. No. 840,500; and U.S. Pat. Nos. 3,261,655 and 3,219,598. In a preferred group of polyisocyanates the number of free isocyanate groups per molecule will be between 3 and 6. To illustrate the structure of these isocyanates the following typical formulas of polyisocyanates are presented:

H O O H I II II I N-C-N-C-N-CI-l NCO 2 6 (cfi l NCO NCO

at least 1 0 o H NCO n o-c-u- -ca o H NCO II I 2-O-C-N- -CH3 0 H NCO II I -OC-N- An Average of H o HCH3 I II I HC-OCN NCO o HCH I I l-IC-O-C-N- I II ac-o-c- I I II ac-o-c- I II HC-O-C- I II ac-o-c- NCO a o H a II I I -N-c-0-cH c--c-ca II 0 o NCOCH3 O=CA (3:0 I I HN N-H I I Compounds (a), (b), (c) and (d) are known respectively by the trade names Desmodur N, Mondur R, PAH and Mondur CB.

Polyisocyanate (e) is prepared by reacting an excess (50% excess) of toluene 2,4-diisocyanate (2,4-tolylene diisocyanate) with sorbitol in a nitrogen atmosphere at a temperature between about 70C. to 80C. The unreacted (excess) diisocyanate is removed by extraction with Stoddard solvent. Polyisocyanate (f) is prepared by reacting erythritol with a 50% excess of toluene 2,6- diisocyanate in a nitrogen atmosphere at a temperature of about 75C. to 80C. and the unreacted diisocyanate is extracted with Stoddard solvent.

The hydroxyl terminated ethylenically unsaturated esters used to prepare the monomers of Formula (1) above are monohydroxyl terminated ethylenically unsaturated esters and can be made by condensing any one of a large variety of ethylenically unsaturated acids with a suitable diol reactant.

In general the preparation of the present hydroxyl terminated unsaturated ester is carried out by condensing a suitable unsaturated acid with a small molar excess of a suitable diol. For example. a mol ratio of diol to acid of from about l.l:l to l.3:l can he used but a ratio of diol to acid of about l:l is preferred. ln the preparation of the subject monoester the condensation reaction between the diol and acid can be carried out in the presence ofa catalytic amount ofany of the well known condensation or esterification catalysts such as p-toluene-sulfonic acid. Such a catalyst is generally used at a concentration of from about 0.005% to 0.3% by weight based on the weight of the reaction mixture. This reaction is preferably carried out in the presence of an inert solvent to provide for solution of the reactants. For example, a hydrocarbon solvent such as toluene or xylene can be used. The present condensation reaction can be carried out at the reflux temperature of the reaction mixture. If desired, other reaction additives such as a polymerization inhibitor, for example hydroquinone can be used in conjunction with the subject reaction.

When an acid chloride of the subject unsaturated acids is used to prepare the present hydroxyl terminated ethylenically unsaturated esters, it is preferred that the mol ratio of diol to acid chloride be about 1:1 and no condensation catalyst is needed.

The ethylenically unsaturated monocarboxylic acids that can be used to prepare the subject hydroxyl terminated unsaturated esters are any of such having from about 3 to l8 carbon atoms. For example, among those thatcan be used are sorbic acid, acrylic acid, methyla- CH NCO crylic acid, crotonic acid, ricinoleic acid, oleic acid, linolenic acid, linoleic acid and eleostearic acid. The acid chlorides of these acids can also be used as reactants if desired.

The subject hydroxyl terminated unsaturated esters can also be prepared from lower alkyl (C to C monoesters of unsaturated dicarboxylic acids such as maleic acid and fumaric acid as well as other such acids having from 3 to 18 carbon atoms.

The diol reactants used to prepare the subject hydroxyl terminated unsaturated ester reactants can also be varied greatly. The subject diol reactant can be aliphatic or aromatic and saturated or unsaturated.

Among the aliphatic diols that can be used are the straight or branched chain alkane diols and the cycloaliphatic diols having from 2 to 12 carbon atoms. For example, among those that can be used are ethylene glycol, l,4-butylene glycol, l,6-hexylene glycol, neopentyl glycol, 1,4-cyclohexane dimethanol, hydroxypivalyl hy- 7 8 droxypivalate, 2,5-dimethyl-2,5-hexanediol tetraethylenically unsaturated ester is generally carried out methyl l,3-cyclobutanediol and 2,2-bis(bromoethyl)- in the presence of a catalytic amount of a suitable catapropane-l ,3-diol. lyst such as an organic tin compound. for example di- Any of the known unsaturated aliphatic diols conbutyl tin diacetate. dibutyl tin dilaurate or an amine taining from 2 to 10 carbon atoms can also be used to such as triethylenediaminc. Such catalysts are generally prepare the subject hydroxyl terminated unsaturated employed ata concentration from about (LOW! to 0.5% ester reactants. For example, among those that can be by weight based on the weight of the reaction mixture. used are the monoallyl ether of glycerin, diallyl ether Other reaction aids. for example, polymerization inhibof pentaerythritol, hydroxyl terminated butadiene coitors such as hydroquinone can also be used in the polymers and dimethyl hexynediol. preparation of the subject urethane monomers. The Among the aromatic diols that can be used to presubject reaction used to prepare the present urethane pare the subject hydroxyl terminated unsaturated ester monomers is generally carried out at a temperature reactants is the diol represented by Formula(2) above. within the range of 40C. to 100C. at atmospheric Examples of hydroxyl terminated ethylenically unsatpressure in an inert atmosphere such as nitrogen. In any urated esters that can be used to prepare the urethane 5 event the reaction temperature must be sufficient so as monomers of Formula (1) above are l-hydroxyethyl to drive the reaction to completion. acrylate, l-hydroxyethyl methacrylate, l-hydroxyhexyl Unsaturated monomers representative of the monooleate, polyoxypropylene (l6) 2,2-bis (4-hydroxymers characterized by Formula (1) are as follows: (g) phenyl)propane monoacrylate, poloxypropylene(4) 2,2-bis (4-hydroxyphenyl)propane monolinolenate, l- (g) CH3 0 O H hydroxyneopentyl lmoleate, l-hydroxypropyl rlcinoleg jj l l ate, l-hydroxyethyl eleostearate, l-hydroxyethyl methv a acrylate, l-hydroxyneopentyl methacrylate and hydroxymethyl cyclohexanemethyl methacrylat wherein R represents the trivalent residue of Desmodur The above described types of polyisocyanates are re- N after e c of its 3 NCO gr p I O CH O H i 2 3 l CH CH-CH C O C CH O C N R H c v 3 acted with a suitable hydroxyl terminated ethylenically wherein R represents the trivalent residue of Mondur unsaturated ester reactant, as exemplified above and R after reaction of its 3 NCO groups (i) (i) o o H" CH CH CH C O (CH 5 OC N R prepared from the above described reactants, to form wherein R is the hexavalent residue of polyisocyanate the monomers of this invention represented by For- (e) listed above after reaction of its 6 NCO groups (j) (j) 0 CH o H n II I CH2 CH C O CH2 C CH2 O C N R i. 3 mula (1) above. wherein R is the tetravalent residue of polyisocyanate The urethane monomers of the present invention are (f) listed above after reaction of its 4 NCO groups (k) k c H o c H o H "i I 2 5 II I 4 9 II I i CH2 C C-O CH2-CH O C N R 3 prepared by reacting a suitable polyisocyanate with 21 wherein R is the trivalent residue of PAH after reaction sufficient quantity of one of the abo e described yofits 3 NCO groups. In order for those skilled in the art droxyl terminated ethylenically unsaturated esters so to r f ll d t d thi i nti th f ll wi that there are essentially no free isocyanate groups ren-limit d xampl s are given maining For example, one mol of the polyisocyanate Examples 1 to 10 illustrate the preparation of several repre ented by formula above iS reacted With three preferred unsaturated resin monomers of the present mols of one of the subject hydroxyl terminated ethyli v nti n enically unsaturated esters to form a product represented by Formula (1) above and as exemplified by EXAMPLE I Formulas (g) to (k) hereinafter. The present reaction 280 grams of styrene, 594.6 grams of the polyis between the polyisocyanate and hydroxyl terminated nate of Formula (a) (Desmodur N), 1.4 grams of hydroquinone, and 1.5 grams of dibutyl tin dilaurate are charged at room temperature to a 3-liter 4-necked flask, equipped with a stirrer, thermometer, nitrogen gas inlet tube, dropping funnel and a condenser. The temperature is then raised to a temperature of about 45 to 50C. and maintained at this temperature and within an hour period 523.6 grams of l-hydroxyethyl methacrylate is added dropwise. The temperature is maintained at 45 to 50C. until the reaction product is found to be essentially free of unreacted isocyanate groups, that is, less than 0.1 percent by weight of the isocyanate groups originally present are still available or free. The styrene solution of this unsaturated urethane trisethyl methacrylate monomer resin is a clear solution.

The percent free isocyanate (NCO) content as given above and in all of the following examples were determined according to the test procedure described in the Union Carbide Corp. publication entitled Urethane Coatings Chemicals, Copyright 1964, F-41 146, pages 24 and 25.

For illustration purposes the preparation of the monomer product of Example 1 can be represented by the following equation:

mixture is then heated at a temperature of from 70 to 85C. and maintained at this temperature until the percent of free isocyanate groups drops below 0.5% by weight of the isocyanate groups originally present in the reaction mixture. The reaction product is a viscous, clear solution of the polyurethane-hydroxyneopentyl methacrylate product.

EXAMPLE 3 173 grams of 1,4-cyclohexanedimethanol, 104.5 grams of methacrylyl chloride, grams of sodium hydroxide, 100 grams of distilled water, 0.2 gram of hydroquinone, and 200 grams of toluene are charged to a l-liter, 4-necked reaction vessel equipped with a con- H O O H I II II I =N-CH NCN-C-N-CH N=C=O+ 0 c 2 6 2 6 N C O (Desmodur N) O CH II I 3 HO CH CH O C C CH (l-hydroxyethyl methacrylate) O H H O O H H O 0 CH .1! I I II II I I II II I ('IH CH -OCN- (CH -NCI:l-C-N- (CH N-CO-CH CH OCC CH c O N-H 9 CH 9 O 9 (11-1 CH O-CH CH O-C-C EXAMPLE 2 177.5 grams of neopentyl glycol, 122.5 grams of methacrylic acid, 0.15 gram of hydroquinone and 1.5 grams of p-toluene-sulfonic acid are charged to a one liter, 4-necked reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube and a water trap condenser combination. At this point, 200 grams of xylene are poured through the condenser so as to fill the water trap. Any excess xylene is allowed to flow into the reaction vessel. The mixture is then heated to its reflux temperature and the reaction allowed to proceed at reflux until the theoretical amount of water (25.6 milliliters) is obtained. The resulting lhydroxyneopentyl methacrylate-xylene blend is then denser, thermometer and nitrogen inlet tube. The reaction is carried out at the reflux temperature of the reaction mixture. After the completion of the reaction, the

product, hydroxymethylcyclohexanemethyl methacrylate is separated from the toluene and water by distillation.

234.5 grams of the above prepared ester product is then reacted according to the procedure of Example 2 with 255.5 grams of a polyisocyanate corresponding to Formula (d) above (Mondur CB) in the presence of 0.35 gram of hydroquinone and 1.0 gram of triethylene diamine. The reaction is carried out at to C. until a test for free isocyanate groups shows none present. The resulting monomer product can be represented by the following formula:

9 3 (DI l;I N-C-OCIl -CH2OC-C CH2 CH2O-C'-N- CH3 *3 .3 .3 (3 1 1 N-C-O-CH Q CH -OCC CH CH CH -C CH -O-C-N- CH 9 9 5 9 Ill N--C--O--CH2 -CH2-OC-C CH2 CH2OC-N- CH3 EXAMPLE 4 ture. The resulting monomer is a viscous liquid.

According to the procedure of Example 3, 298.5

CH3(CH2)4-C c CH2 H H O I v u According to the procedure of Example 2, 1398 EXAMPLE 6 To a 4-necked, 2 liter flask equipped with mechanical stirrer, nitrogen inlet tube, thermometer, condenser and water trap, 520 grams of monomethylester of fumaric acid, 576 grams of tetramethyl-l,3- cyclobutanediol, 500 grams of xylene p-toluenesulfonic acid are charged at room tempera- H OCH $3 CH CH ture. After 72 ml of water have been collected in the grams of the ester prepared above and 369 grams triwater trap, the resulting fumaric acid diester of methaphenylmethane triisocyanate [Formula (b) above, Mondur R] are reacted at 50 to 70C. until the reaction mixture is found to have less than 0.5% by weight of the isocyanate groups originally present in the reaction mixture. The resulting product is a highly viscous, resinous product.

EXAMPLE 5 130 grams of the half ester of fumaric acid and methanol are reacted with 144 grams of tetramethyl 1,3- cyclobutanediol according to the procedure of Example 2 at their reflux temperature until the theoretical water of esterification has been recovered and the following product is formed:

211.2 grams of the above prepared hydroxyl terminated ethylenically unsaturated ester is reacted with 109 grams of polymethylene polyphenyl isocyanate with an equivalent weight of 132 [known under the tradename of PAH and represented by Formula (c) above] at a temperature of 80 to 85C. in a one liter, 4-necked flask until the reaction product is essentially free of free isocyanate groups, that is, there is less than 0.5 weight percent free isocyanate present based on the original isocyanate group present in the reaction mixnol and tetramethyl-l,3-cyclobutanediol is washed to remove the catalyst and then stripped free of xylene. Then 1080 grams of the above prepared fumaric diester, 400 grams of butyl methacrylate, and 2 grams of zinc naphthenate are charged to a suitable 4-necked, round bottom flask equipped with stirrer, gas inlet tube, thermometer, condenser and the mixture is slowly heated to 60C. under a nitrogen atmosphere. Then 520 grams of Mondur R (triphenylmethane triisocyanate) is added over a 1 hour period. The reaction is terminated when the percent free isocyanate group (NCO) content is below 0.5% by weight of the isocyanate groups originally present in the reaction mixture.

The unsaturated urethane is a 80% solution in butyl methacrylate. The solution is clear and viscous.

EXAMPLE 7 and 1 gram of monolinolenate is an oily liquid, of light yellow color and has a viscosity of 250 cps at 25C; The hydroxyl number of the unsaturated monohydroxy ester is 125. Then to a second 1 liter round bottom flask equipped with mechanical stirrer, gas inlet tube, thermometer, condenser and dropping funnel is charged 178.8 grams of the neopentyl glycol monolinolenate. The hydroxy ester is heated to 60C. under a nitrogen atmosphere. Then over a 1 hour period 181.2 grams of PAP] (polymethylene polyphenyl isocyanate) is added from the dropping funnel. The exothermic reaction mixture is maintained at 6070C. and when all the PAP] is O H N-C-'O--CH-CH II I 2 CH -O-CN- CH added the temperature is increased to 100C. for 1 hour after which time the free isocyanate group content is less than 0.5% by weight of the isocyanate groups originally present in the reaction mixture. The unsaturated urethane monomer is a dark brown, viscous resin.

EXAMPLE 8 To a 1 liter, 4-necked round bottom flask equipped with stirrer, nitrogen inlet, thermometer, condenser and Dean Stark water trap is charged 540 grams of polyoxypropylene( l6)-2,2-bis (4-hydroxyphenyl)propane, 36 grams of acrylic acid, 0.5 gram-of p-toluenesulfonic acid and 100 grams of xylene and heated to re- Product A CH H CH I II I 3 y 3 n O H N-C-O- CH-CH O- -C- -O- CH -CH- O-C-CH=CH 2 2 2 sented by Formula (d) above and 1 gram of dimethylethanolamine. When the isocyanate is dissolved, the reaction mixture is heated to 60C. under a nitrogen atmosphere over a 1 hour period. Then 35l.6 grams of the above prepared monoester is added while the exonally present in the reaction mixture. The unsaturated urethane solution is a clear viscous liquid. The resulting product can be represented by the following formula:

CH CH 0 EXAMPLE 9 To a 1 liter, 4-necked, round bottom flask equipped with stirrer, nitrogen inlet tube, thermometer, water trap and condenser is charged at room temperature,

232 grams of fumaric acid, 116 grams allyl alcohol, 3

grams p-toluenesulfonic acid and 100 grams of xylene. The water trap is filled with xylene. The resulting reaction mixture is heated at reflux until 36 ml of water is collected. The product is then washed with water to remove the catalyst. Then the xylene is stripped from the 212 grams of the above prepared Product A, 208 grams of neopentyl glycol, 1 gram p-toluenesulfonic acid, grams of xylene and 0.5 gram hydroquinone are charged to a 1 liter, 4-necked flask equipped with a nitrogen inlet, thermometer and condenser. The resulting mixture is refluxed until 36 ml of water is ob-.

tained. Then the xylene is stripped from the reaction product mixture. The unsaturated hydroxyester ob- Product B CH I 3 16 tained is a clear, oily liquid and is represented by the products of the present invention can be used in the following formula: preparation of molded plastic products and glass fiber or other synthetic polymer fiber reinforced plastic products such as pipes, gasoline tanks, boats, duct work, storage tanks and laminates.

The mixed resin products of the present invention are comprised of the reaction products of the urethane O O CH3 monomers of this invention and ethylenically unsatu- To a 1 liter, 4-necked flask equipped with stirrer, rated polyesters, and/or other ethylenically unsaturated thermometer, nitrogen inlet, dropping funnel, and conhomopolymerizable monomers.

denser is charged 363 grams of Product B above, 0.5 Examples 1 1 through 20 illustrate the preparation of gram hydroquinone and 0.5 gram of dimethylethanolaresins, moldings and laminates using urethane monomine at room temperature. The resulting reaction mixmers of this invention by themselves or in conjunction ture is slowly heated to 60C. and within minutes, with a polyester, an ethylenically unsaturated monol84.5 grams of Mondur R is added and the resulting 15 mer, or a combination of both. The reactants used in mixture is maintained at a temperature from C. to preparing these resinous products can be mixed by me- C. When the addition is complete, the resulting mixchanical means, such as mechanical stirring, a ball mill, ture is heated for 1 hour at C. after which time the or other mixing or blending devices, to a uniform solupresent free isocyanate group content is below 0.5% by tion. To this mixture is then added a conventional curweight of the isocyanate groups originally present. The 20 ing system, that is, one or more catalysts and optionally unsaturated urethane monomer is a viscous clear resin promoters for an addition reaction and polymerization and can be represented by the following formula: inhibitors if indicated. The resulting reaction mixture Product C CH I H C -N-C-O-CH C-CH OCCH=CHC-OCH CH=CH I II 2 I 2 II II 2 2 V a V W CB O O 3 EXAMPLE 10 can be reacted at room temperature or at elevated temperature and at atmospheric pressure. In most in- To a liter, 4-necked flask equipped W h Surfer stances, it has been found desirable to first react the troge" mlet thermometer droppmg funnel and subject reactants at room temperature for about 16 to denser is Charged at room temperature grams of 24 hours, and then post cure the resulting product at y gram of hydroquinone, 04 gram dlbulyl tin temperatures within the range of 80C. to C. for I dllaurate and 233-2 grams of Desmodur N represented 35 to 6 hours. Obviously, these cure temperatures and rey Formula above The reaction mixture is action times can be suitably varied widely depending heated to 60C. under nitrogen flow and within 1 hour on th t fi i h d product desired and its end use.

356.8 gram of m no llyl e her f glyc ne m n Among the ethylenically unsaturated monomers that methacrylate is added over a 1 hour period. Th e can be copolymerized with the subject urethane monotemperature is raised to 90C. until the percent isocya- 40 mers represented by formula (I) are any of the well ate group Content is be o 0.5 by We ght o the i known vinyl monomers such as styrene and divinylbencyanate gr ups originally present. The resulting urezene. In addition any of the other well known suitable thane monomer solution in styrene is a clear liquid and vinyl monomers can be used, for example, acrylonitrile, can be represented by the following formula: glycidyl methacrylate, hydroxyalkylmethacrylate,

O H H O O H O II I I II II I II -N N N-CN CH NCOCH-CH O-C-C=CH /caoc (cn c I 2 2 CH2 CH2 (CH2) 6 H 0 CH2 CH3 0 0 NH o I I I I cn 2 o c 0 CH CH=CH CH C-CH3 0 II II I CH2 CH2 (EH-CH 2-O-CH2-CH=CH2 C CH II 3 The subject urethane monomer resins and the homo stearylmethacrylate, tertiary butyl styrene. vinyl aceand copolymer products thereof and the mixed resin tate and n-vinyl pyrrolidone. Such vinyl monomers can also be copolymerized with the copolymers resulting from the polymerization of a urethane monomer of the present invention with a suitable unsaturated polyester resin as described hereinabove.

The resin or polymer products of the present invention can contain monomer units derived from any of the hereinabove described monomers and polymers. For example, the polymerizable unsaturated urethane compounds represented by Formula (1) above can be homopolymerized or copolymerized with any ratio or mixture of monomers coming within Formula (1). Other resin products of the present invention can contain 0.5% to 95% of polymer segments derived from suitable ethylenically unsaturated polyester resins, as described hereinabove, and 0.5% to 95% of polymer segments derived from one or more of the unsaturated urethane monomers represented by Formula (1) above. In addition, the resin products of the present invention include those prepared from any combination of the above described monomers or resins in combination with sufficient quantity of a suitable vinyl monomer so that up to 50% of the resulting polymer segments are derived from said vinyl monomer, such as illustrated above, for example styrene.

Any of the well known catalysts or curing systems conventionally used in the addition polymerization of ethylenically unsaturated monomers such as herein involved can be utilized to prepare the subject homo and copolymeric resin products. For example, catalytic amounts of catalysts such as benzoyl peroxide, tertiary butyl peroxide and methyl ethyl ketone peroxide can be used. These catalysts are generally used at a concentration of from about 0.5% to 3.0% based on the weight of the reactants. Reaction promoters such as dimethyl aniline and cobalt naphthenate can be utilized in catalytic amounts along with one of the above-mentioned catalysts. In addition any of the other well known reaction modifiers can be incorporated with the subject reaction mixtures when indicated. For example, a reaction inhibitor such as tertiary butyl catechol can be used.

EXAMPLE l1 Copolymer of Monomer of Example 1 with Styrene In a polyethylene cup, 75 grams of the monomer resin solution of Example 1, 25 grams styrene, 1 gram benzoyl peroxide and 0.2 gram of dimethylaniline are mixed together with a spatula. The water white clear solution has a viscosity at 25C. of 77 cps. After deaerating the solution is poured into a 4; inch glass mold and cured at room temperature for 24 hours, followed by a postcure at 100C. for 4 hours.

The catalyzed solution had a gel time of 7 minutes, a gel to peak time of 9-minutes, and a peak exotherm temperature of 210C. as determined by the SP1 method. This SPI method for reactivity rate or cure time is described in The Society of the Plastics Industry Inc. book of Reinforced Plastics by Samuel Oleesky and J. G. Mohr, Reinhold Publishing Co. 1964. The cured casting had the following properties:

Flexural strength. PSI 17.200 Flcxural modulus. 10 0.41 Bareol hardness 28-31 Heat distortion. C. 95 Tensile strength. 10300 Tensile modulus. 0.42 Percent Elongation 8.87 Charpy impact 6.77

EXAMPLE l2 Copolymer of Monomer of Example 1 with Styrene and Polyoxypropylene(2.2)-2.2-bis(4-Hydroxyphenyl)- Propane Fumarate In a polyethylene cup, 25 grams of a mixture of 50% polyoxypropylene(2.2)-2,2'-bis(4-hydroxyphenyl)propane fumarate and 50% styrene, plus 28.1 grams styrene and 46.9 grams of the unsaturated urethane solution of Example 1, 1 gram benzoyl peroxide and 0.2 gram of dimethyl aniline are thoroughly mixed. This solution at 50% solids has a viscosity of 81 cps. at 25C. and is yellowish. After deaerating, the mixture is poured into a A; inch glass mold, cured for 24 hours at room temperature and post cured 4 hours at C. The casting had the following properties as determined by the same ASTM tests used to evaluate the product of Example 112 Flexural Strength PSI 16100 Flexural modulus. 10 0.41 Barcol Hardness 20-23 Heat Distortion C. 97 Tensile Strength. PS] 9900 Tensile Modulus. 10 0.43 Percent Elongation 8.50 Charpy Impact 5.51

EXAMPLE 13 Copolymer of Monomer of Example 1 with Styrene and Polyoxypropylene(2.2)-2,2-bis(4-Hydroxypheny1)- Propane Fumarate In a polyethylene cup, 50 grams of a mixture of 50% polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane fumarate and 50% styrene, plus 18.7 grams styrene, 31.3 grams of the unsaturated urethane solution of Example 1, 1 gram benzoyl peroxide and 0.2 gram dimethyl aniline are thoroughly mixed. At 50% solids this solution has a viscosity of 158 cps at 25C. and the following cure times as determined by the SP1 method or reactivity test referred to hereinabove: gel time 26 minutes, gel to peak time 12 minutes, peak temperature 216C. After deaerating, the catalyzed solution is poured into a it; inch glass mold and cured for 24 hours at room temperature and post cured 4 hours at 100C. The casting had the following properties as determined by the same ASTM tests used to evaluate the product of Example 11:

Flexural Strength. PSI

EXAMPLE 14 Homopolymer of Monomer of Example 3 In a polyethylene cup, 100 grams of the monomer resin of Example 3 is mixed with 1.5 grams ofa 60% solution of methyl ethyl ketone peroxide in dimethyl phthalate, 1% cobalt naphthenate, 0.2 gram dimethylaniline and 0.04 gram tertiary butyl catechol. The mixture had the following cure times as determined by the SP1 method referred to hereinabove: gel time 40 minutes, gel to peak time 11 minutes, and peak exotherm 209C. After deaerating, the catalyzed urethane monomer is poured in a 74; inch glass mold, cured for 24 hours at room temperature and 4 hours at 100C. The casting is a tough, clear, thermoset plastic.

EXAMPLE l5 l-lomopolymer of Monomer of Example 5 In a polyethylene cup, 100 grams of the monomer- EXAMPLE l6 Copolymer of Styrene Solution of Monomer of Example 1 and a Butyl Methacrylate Solution of the Monomer of Example 6 In a polyethylene cup, 50 grams of unsaturated urethane solution in styrene of Example 1 and 50 grams of unsaturated urethane solution in butyl methacrylate of Example 6 are mixed together with 1.0 gram benzoyl peroxide and 0.2 gram of dimethyl aniline. The mixture is poured into a a inch glass mold, cured for 24 hours at room temperature and post cured for 4 hours at 100C. After curing, a clear transparent glass-like thermoset casting is obtained.

EXAMPLE 17 Laminate of Copolymer of Polyoxypropylene (2.2)-2,2-bis(4-1-1ydroxyphenyl)Propane Fumarate,

Styrene and Monomer of Example 1 A laminate is prepared by copolymerizing a 50% solution of p0lyoxypropylene(2.2)-2,2'-bis(4-hydroxyphenyl)propane fumarate in styrene with the monomer resin solution of Example 1 and styrene following the SP1 lay-up method (as described under ASTM-G581- 68) of 1 layer Owens Corning Fiberglass (C-glass), 2 layers fiber glass chopped strand (E-glass) mat, and 1 layer C-glass. The laminate is made between 2 layers of Mylar polyester film. In a suitable container, 195.2 grams of a mixture of 50% polyoxypropylene(2.2)- 2,2'-bis(4-hydroxyphenyl)propane fumarate and 50% styrene plus 220 grams of styrene, 367 grams resin solution of Example 1, 3.9 grams of benzoyl peroxide and 1.17 grams of dimethyl aniline are mixed. The glass/resin laminate was prepared from this solution and a combined weight of C-glass and chopped mat of 237 grams. The laminate was cured for 24 hours at room temperature and 4 hours at 100C. The laminate had the following properties as determined by the same ASTM tests used to evaluate the product of Example 1 1:

Percent glass" 26% Tensile strength PS1 13400 Tensile modulus 0.98 Percent break elongation 2.03 Flexural strength PS1 15700 Flcxural modulus 10" 0.74 Barcol hardness 35-40 EXAMPLE 18 Molding Compound Copolymer of Monomer of Example 7, Styrene and Divinyl benzene 72.13 grams of the monomer resin of Example 7 are mixed with l 1.5 grams of styrene and 10 grams divinylbenzene. To this solution then is added 0.03 gram of ditertiarybutylhydroquinone, 0.28 gram of benzoyl peroxide, 0.94 gram of tertiarybutyl perbenzoate, 0.47 gram triphenyl phosphite and 4.66 grams of aluminum stearate.

39.2 grams of the above mixture are then blended with 30.8 grams calcium carbonate Surfex MM, and 30 grams Owens Corning /a inch chopped glass fibers. The resulting molding compound was molded into M; inch thick pieces at 300F. under 2000 psi pressure. The molded plastic (per the above noted ASTM tests Example 1) had a Barcol hardness of 70, flexural strength 17,000 PS1, flexural modulus 1610, tensile strength 8000 PSI, lzod impact 12 and HDT (Heat Distortion Temperature) 300F.

EXAMPLE l9 Copolymer of Monomer of Example 9 With Polyoxypropylene(2.2)-2,2-bis(4-Hydroxyphenyl)- Propane Fumarate and Styrene To a polyethylene cup is charged 40 grams of the monomer resin of Example 9, 50 grams of a mixture of 50% polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane fumarate and 50% styrene plus 10 grams of styrene, 1 grams of benzoyl peroxide and 0.1 gram of dimethyl aniline and mixed thoroughly. Then after deaerating, the mixture is poured into a 42 inch glass mold and cured for 24 hours at room temperature followed by 4 hours at C. The resulting casting is a tough, clear thermoset resin.

EXAMPLE 20 Copolymer of Monomers of Examples 10 and 3 and Styrene In a polyethylene cup is mixed the following: 50 grams of the monomer resin of Example 10, 10 grams of styrene and 40 grams of the monomer resin of Example 3, 1.2 grams benzoyl peroxide, 0.1 gram dimethyl aniline. Then after deaerating, the mixture is poured into a glass mold having a depth of A; inch and cured at room temperature for 1 hour and 4 hours at 100C. The resulting casting is a clear transparent plastic.

1 claim:

1. A polymerizable urethane compound which is the reaction product of a. an organic polyisocyanate having at least 3 isocyanate groups, and

b. a stoichiometric quantity of a hydroxyl terminated ethylenically unsaturated ester reaction product of an ethylenically unsaturated monocarboxylic acid having from 3 to 18 carbon atoms and an etherified diphenol represented by the formula wherein z is 0 or 1; R is an alkylene radical containing 1 to 5 carbon atoms, oxygen, sulfur or a divalent radical which may be represented by the following formulas:

l l R, is ethylene or propylene; each E is individually selected from the hydrogen atoms and halogen atoms, and x and y are integers from 1 through about 20 with the proviso that the sum ofx and y is from about 2 through about 30, for reacting with each of said isocyanate groups wherein the reaction between reactants (a) and (b) is carried out at a temperature within the range of 40C. to 100C.

at atmospheric pressure in an inert atmosphere.

2. A compound of claim ll wherein (a) has 3 isocyanate groups.

3. A compound of claim 2 wherein (b) is the reaction product of oxyalkylated 4,4'-isopropylidenediphenol and an ethylenically unsaturated monocarboxylic acid.

4. A compound of claim 1 wherein (b) is a stoichiometric quantity of a hydroxyl terminated ethylenically unsaturated reaction product of acrylic acid or methacrylic acid and an etherified diphenol represented by the formula wherein z is 0 or 1; R is an alkylene radical containing 1 to carbon atoms, oxygen. sulfur or a divalent radical which may be represented by the following formulas:

phenol is an oxyalkylated 4,4-isopropylidenediphenol.

6. A compound of claim 4 wherein the etherified diphenol is polyoxypropylene(2.2)-2,2'bis(4- hydroxyphenyl) propane.

7. A compound of claim 1 wherein the ethylenically unsaturated carboxylic acid is selected from the group consisting of sorbic acid, crotonic acid, ricinoleic acid,

oleic acid, linolenic acid, linoleic acid, and eleostearic acid.

UNITED STATES PATENT OFFICE CERTIFICATE OF CGRRECTION PATENT NO. 3 856 830 DATED December 24, 1974 lNVENTOR($/) Erich Kuehn It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 16 now reads:

amounts to enhance to activity of the particular reacshould read:

amounts to enhance the activity of the particular reac- Column 19, line 18, now reads:

into a glass mold having a depth of q one-eight inch should read:

into a glass mold having a depth of one-eight inch Claim 7, second line, i now reads:

unsaturated carboxylic acid is selected from the group should read:

unsaturated monocarboxylic acid is selected from the group Signed and Scaled this Fifth Day of October 1976 [SEAL] Arrest.

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner of Patents and Trademarks 

1. A POLYMERIZABLE URETHANE COMPOUND WHICH IS THE REACTION PRODUCT OF A. AN ORGANIC POLYISOCYANATE HAVING AT LEAST 3 ISOCYANATE GROUPS, AND B. A STOICHIOMETRIC QUANTITY OF A HYDROXYL TERMINATED ETHYLENICALLY UNSATURATED ESTER REACTION PRODUCT OF AN ETHYLENICALLY UNSATURATED MONOCARBOXYLIC ACID HAVING FROM 3 TO 18 CARBON ATOMS AND AN ETHERIFIED DIPHENOL REPRESENTED BY THE FORMULA
 2. A compound of claim 1 wherein (a) has 3 isocyanate groups.
 3. A compound of claim 2 wherein (b) is the reaction product of oxyalkylated 4,4''-isopropylidenediphenol and an ethylenically unsaturated monocarboxylic acid.
 4. A compound of claim 1 wherein (b) is a stoichiometric quantity of a hydroxyl terminated ethylenically unsaturated reaction product of acrylic acid or methacrylic acid and an etherified diphenol represented by the formula
 5. A compound of claim 4 wherein the Etherified diphenol is an oxyalkylated 4,4''-isopropylidenediphenol.
 6. A compound of claim 4 wherein the etherified diphenol is polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl) propane.
 7. A compound of claim 1 wherein the ethylenically unsaturated carboxylic acid is selected from the group consisting of sorbic acid, crotonic acid, ricinoleic acid, oleic acid, linolenic acid, linoleic acid, and eleostearic acid. 